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2,354 results on '"Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)"'

1. Influence of Sintering Conditions on the Structure and Redox Speciation of Homogeneous (U,Ce)O2+δ Ceramics: A Synchrotron Study

Author

Malvina Massonnet, Laurent Claparede, Julien Martinez, Philippe M. Martin, Myrtille O.J.Y. Hunault, Damien Prieur, Adel Mesbah, Nicolas Dacheux, Nicolas Clavier, Interfaces de Matériaux en Evolution (LIME), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Institut des Sciences et technologies pour une Economie Circulaire des énergies bas carbone (ISEC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Helmholtz-Zentrum Dresden-Rossendorf (HZDR), European Synchroton Radiation Facility [Grenoble] (ESRF), Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Inorganic Chemistry, XAS, O/M ratio, nuclear fuel, structure, uranium oxide, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Physical and Theoretical Chemistry, [CHIM.RADIO]Chemical Sciences/Radiochemistry
Abstract

International audience; Although uranium–cerium dioxides are frequently used as a surrogate material for (U,Pu)O2−δ nuclear fuels, there is currently no reliable data regarding the oxygen stoichiometry and redox speciation of the cations in such samples. In order to fill this gap, this manuscript details a synchrotron study of highly homogeneous (U,Ce)O2±δ sintered samples prepared by a wet-chemistry route. HERFD-XANES spectroscopy led to determining accurately the O/M ratios (with M = U + Ce). Under a reducing atmosphere (pO2 ≈ 6 × 10–29 atm at 650 °C), the oxides were found to be close to O/M = 2.00, while the O/M ratio varied with the sintering conditions under argon (pO2 ≈ 3 × 10–6 atm at 650 °C). They globally appeared to be hyperstoichiometric (i.e., O/M > 2.00) with the departure from the dioxide stoichiometry decreasing with both the cerium content in the sample and the sintering temperature. Nevertheless, such a deviation from the ideal O/M = 2.00 ratio was found to generate only moderate structural disorder from EXAFS data at the U-L3 edge as all the samples retained the fluorite-type structure of the UO2 and CeO2 parent compounds. The determination of accurate lattice parameters owing to S-PXRD measurements led to complementing the data reported in the literature by various authors. These data were consistent with an empirical relation linking the unit cell parameter, the chemical composition, and the O/M stoichiometry, showing that the latter can be evaluated simply within a ± 0.02 uncertainty

Published
2023

2. When Ions Defy Electrostatics: The Case of Superchaotropic Nanoion Adsorption

Author

Max Hohenschutz, Jean-François Dufrêche, Olivier Diat, Pierre Bauduin, Ions aux Interfaces Actives (L2IA), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), and Modélisation Mésoscopique et Chimie Théorique (LMCT)

Subjects
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, General Materials Science, Physical and Theoretical Chemistry
Abstract

International audience; Nanometer-sized anions, like polyoxometalates and borate clusters, bind to nonionic hydrated matter driven by the chaotropic effect, which arises from the favorable dehydration of the ions. Herein, we evaluate the adsorption and activity coefficient of the superchaotropic Keggin polyoxometalate SiW12O404– (SiW) on nonionic surfactant (C8E4) micelles by modeling small-angle X-ray and neutron-scattering spectra. Neither hard sphere nor electrostatic repulsion models reproduce the experimental activity coefficient of adsorbed SiW ions on the micelles. However, the activity and binding of SiW on the micelles is well-described by a Langmuir adsorption isotherm. These results imply that adsorbed SiW ions are non-interacting and “create” around themselves adsorption sites on the micelle. The temperature dependence of the adsorption constant showed that the SiW adsorption is enthalpically driven and entropically unfavorable, in line with the typical chaotropic thermochemical signature. The adsorption enthalpy can be split into an electrostatic term and a water-recovery term to evaluate and qualitatively predict the superchaotropicity of a nanoion.

Published
2023

3. Aggregating fluids under centrifugal fields

Author

Stemplinger, Simon, Zemb, Thomas, Horinek, Dominik, Dufrêche, Jean-François, Universität Regensburg (UR), Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), and Modélisation Mésoscopique et Chimie Théorique (LMCT)

Subjects
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry
Abstract

International audience; We present a general theoretical framework designed to interpret the effect of centrifugation of ternary fluids that exhibit weak aggregation. The model includes a buoyancy term with thermodynamic description given by a Flory-Huggins model of ternary systems containing a hydrotrope. The system octanol-ethanol-water used as a numerical example is one of several ternary systems that exhibit dynamic aggregates even far from the critical point and undergo a spontaneous emulsification upon dilution with water (Ouzo effect). The model proposes an explanation from first principles of an increased responsiveness to the centrifugal fields. We illustrate the usage of this system in intensified extraction efficiency of hydrophobic solutes that is at the basis of the dispersive liquid-liquid extraction, and show that its capabilities can be extended from analytical to continuous preparative extraction.

Published
2023

4. Exploring the Aggregation Behavior of Extractant Molecules in Ionic Liquids: A Coupled Polarizable Molecular Dynamics and SAXS Study

Author

Le Crom, Sébastien, Dourdain, Sandrine, Pellet-Rostaing, Stéphane, Duvail, Magali, Modélisation Mésoscopique et Chimie Théorique (LMCT), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), and ANR-16-IDEX-0006,MUSE,MUSE(2016)

Subjects
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry
Abstract

International audience; This study presents a comprehensive investigation of the aggregation behavior of a malonamide extractant molecule (N,N′-dimethyl,N,N′-dioctylhexylethoxymalonamide (DMDOHEMA)) in three different solvents, including two piperidinium- and (trifluoromethylsulfonyl)imide-based ionic liquids (1-ethyl-1-butylpiperidinium bis(trifluoromethylsulfonyl)imide ([EBPip+][NTf2–]) and 1-ethyl-1-octylpiperidinium bis(trifluoromethylsulfonyl)imide ([EOPip+][NTf2–])) and n-dodecane. By combining polarizable molecular dynamics simulations and small-angle X-ray scattering experiments, we extensively investigated the arrangement of supramolecular assemblies of the extractant molecules. Our results showed that the insertion of the alkyl chains of the extractant molecules into the apolar domain of [EOPip+][NTf2–] has a significant impact on the aggregation behavior of the extractant molecules, leading to the formation of smaller aggregates having a higher dispersion compared to other solvents. These findings provide new insights into the physicochemical properties of this type of system and are crucial in designing more effective solvents for rare earth metal extraction.

Published
2023

5. Contribution of Molecular Dynamics in pNMR for the Structural Determination of AnV and AnVI Complexes in Solution

Author

Clovis Poulin-Ponnelle, Magali Duvail, Thomas Dumas, Claude Berthon, Laboratory of Interactions Ligand-Actinide (LILA), Département de recherche sur les procédés pour la mine et le recyclage du combustible (DMRC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Modélisation Mésoscopique et Chimie Théorique (LMCT), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), and ANR-17-CE06-0010,ACTIpNMR,déplacements de RMN paramagnétiques pour les actinides : au délà du modèle des lanthanides(2017)

Subjects
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Inorganic Chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, [CHIM.RADIO]Chemical Sciences/Radiochemistry
Abstract

International audience; In this study, we propose to use classical molecular dynamics (MD) coupled with $^1$H NMR spectroscopy to study the conformations of different actinyl An$^{VI}$ (An = U, Np, and Pu) and An$^{V}$ (An = Np) complexes with tetra-ethyl dyglicolamide (TEDGA) ligands in order to have a better representation of such complexes in solution. Molecular dynamics simulations showed its effectiveness in interpreting the experiments by the calculation of geometric factors needed for the determination of magnetic properties of these complexes. We demonstrated that different conformations of the An$^{V}$ and An$^{VI}$ complexes with TEDGA exist in solution with different coordination modes, which is experimentally confirmed by $^1$H NMR and EXAFS spectroscopies. Furthermore, MD simulations provide additional insights into the structures of complexes in solution since conformations with fast exchanges, which are not accessible from NMR experiments, have been observed by MD simulations.

Published
2022

6. Controlling polyHIPE Surface Properties by Tuning the Hydrophobicity of MOF Particles Stabilizing a Pickering Emulsion

Author

Lorignon, Fabrice, Gossard, Alban, Medjouel, Sabrine, Carboni, Michaël, Meyer, Daniel, Systèmes HYbrides pour la Séparation (LHyS), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Département de recherche sur les procédés pour la mine et le recyclage du combustible (DMRC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)

Subjects
[CHIM]Chemical Sciences
Abstract

International audience

Published
2023

7. Toward a method of understanding the complexation of rare earth element by functionalized organosilanes in aqueous media

Author

Oliver Walker, Diane REBISCOUL, Michael Odorico, Samuel Tardif, Stephane Pellet-Rostaing, Guilhem Arrachart, Etude de la Matière en Mode Environnemental (L2ME), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), and Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM)

Subjects
Colloid and Surface Chemistry, [CHIM]Chemical Sciences
Abstract

International audience

Published
2023

8. Role of molybdenum on the structure and properties of A2O-P2O5-MoO3 (A = Na, Ag, Rb, Cs) glasses

Author

Bodiang, Kadiali, Delevoye, Laurent, Podor, Renaud, Mear, François, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Etude de la Matière en Mode Environnemental (L2ME), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), and Université de Montpellier (UM)

Subjects
Phosphate glass, Thermal properties, Materials Chemistry, Ceramics and Composites, 95Mo-NMR, HT-ESEM, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Condensed Matter Physics, Crystallization, Electronic, Optical and Magnetic Materials
Abstract

International audience; Molybdenum phosphate glasses are materials of interest for nuclear waste storage and solid-state electrolytes, amongst others. Thermal and electrical properties of vitreous molybdophosphates are highly dependent on molybdenum local environment while for example the coordination of this transition metal is still a matter of discussion. The structure of glasses of following composition, xMoO3-(100-x)APO3 (with A = Ag, Na, Rb and Cs) was investigated by means of 31P and 95Mo Nuclear Magnetic Resonance spectroscopy. The structural information was used to better understand the evolution of thermal properties as a function of the molar fraction of MoO3. Particular attention was paid to the crystallization mechanism, studied by X-ray Diffraction, High Temperature Environmental Scanning Electronic Microscopy and Kissinger model, highlighting the formation of a molybdate network (Mo-O-Mo bonds).

Published
2023

9. Liquid–Liquid Flow at Nanoscale: Slip and Hydrodynamic Boundary Conditions

Author

Lolita Hilaire, Bertrand Siboulet, Sophie Charton, Jean-François Dufrêche, Département de recherche sur les procédés pour la mine et le recyclage du combustible (DMRC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Modélisation Mésoscopique et Chimie Théorique (LMCT), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), and Université de Montpellier (UM)

Subjects
Electrochemistry, [CHIM]Chemical Sciences, General Materials Science, Surfaces and Interfaces, Condensed Matter Physics, Spectroscopy
Abstract

International audience; Nonequilibrium molecular dynamics (NEMD) simulations have been performed to describe the flow of a fluid nanolayer confined by another fluid. The results show that the behavior of liquids can still be described by the Navier–Stokes equation at the nanoscale, i.e., when only few molecular layers are involved. NEMD furthermore gives additional knowledge on flow. Indeed, while a very small slip is evidenced for a solid–liquid interface as, e.g., in lubrication, the slip lengths are significantly larger at the liquid–liquid interface, as encountered, e.g., in droplet coalescence. The slip lengths of the two fluids are linked. The increase in hydrodynamic slip for liquid–liquid interfaces is attributed to the enhancement of fluid diffusion, which reduces friction.

Published
2023

10. How Temperature Rise Can Induce Phase Separation in Aqueous Biphasic Solutions

Author

Gautier Meyer, Ralf Schweins, Tristan Youngs, Jean-François Dufrêche, Isabelle Billard, Marie Plazanet, Laboratoire Interdisciplinaire de Physique [Saint Martin d’Hères] (LIPhy ), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Université Grenoble Alpes (UGA), Institut Laue-Langevin (ILL), ​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​ISIS Neutron and Muon Source (ISIS), STFC Rutherford Appleton Laboratory (RAL), Science and Technology Facilities Council (STFC)-Science and Technology Facilities Council (STFC), Modélisation Mésoscopique et Chimie Théorique (LMCT), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Laboratoire d'Electrochimie et de Physico-chimie des Matériaux et des Interfaces (LEPMI), Institut de Chimie du CNRS (INC)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry]), and ANR-15-IDEX-0002,UGA,IDEX UGA(2015)

Subjects
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, General Materials Science, Physical and Theoretical Chemistry
Abstract

International audience; Ionic-liquid-based acidic aqueous biphasic solutions (AcABSs) recently offered a breakthrough in the field of metal recycling. The particular mixture of tributyltetradecylphosphonium chloride ([P4,4,4,14]Cl), acid, and water presents the unusual characteristic of a lower solution critical temperature (LCST), leading to phase separation upon a temperature rise of typically a few tens of degrees. We address here the microscopic mechanisms driving the phase separation. Using small-angle neutron scattering, we characterized the spherical micelle formation in a binary ionic liquid/water solution and the micelle aggregation upon the addition of acid due to the screening of electrostatic repulsion. The increase in both the acid concentration and the temperature eventually leads to micelle flocculation and phase separation. This last step is achieved through chloride ion adsorption at the surface of the micelle. This exothermic adsorption compensates for the entropic cost, leading to a counterintuitive behavior, and may be generalized to a number of molecular systems with an LCST.

Published
2022

11. Size and structure of hexanuclear plutonium oxo-hydroxo clusters in aqueous solution from synchrotron analysis

Author

Thomas Dumas, Matthieu Virot, Denis Menut, Christelle Tamain, Cyril Micheau, Sandrine Dourdain, Olivier Diat, Laboratory of Interactions Ligand-Actinide (LILA), Département de recherche sur les procédés pour la mine et le recyclage du combustible (DMRC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Sonochimie dans les Fluides Complexes (LSFC), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), and Ions aux Interfaces Actives (L2IA)

Subjects
Nuclear and High Energy Physics, Radiation, Actinide Physics and Chemistry, plutonium, Water, SAXS, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, EXAFS, X-Ray Diffraction, Scattering, Small Angle, clusters, [CHIM.RADIO]Chemical Sciences/Radiochemistry, Instrumentation, Synchrotrons
Abstract

A water-soluble plutonium cluster made of six plutonium atoms decorated by four 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid ligands is characterized by small-angle X-ray scattering (SAXS) and extended X-ray absorption fine structure (EXAFS)., The size and shape of a water-soluble hexanuclear plutonium cluster were probed by combining synchrotron small-angle X-ray scattering (SAXS) and extended X-ray absorption fine structure (EXAFS). A specific setup coupling both techniques and dedicated to radioactive samples on the MARS beamline endstation at Synchrotron SOLEIL is described. The plutonium hexanuclear cores are well stabilized by the 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid ligands and this allows a good evaluation of the setup to probe the very small plutonium core. The results show that, in spite of the constrained conditions required to avoid any risk of sample dispersion, the flux and the sample environment are optimized to obtain a very good signal-to-noise ratio, allowing the detection of small plutonium aggregates in an aqueous phase. The structure of the well defined hexanuclear cluster has been confirmed by EXAFS measurements in solution and correlated with SAXS data processing and modelling. An iterative comparison of classical fit models (Guinier or sphere form factor) with the experimental results allowed a better interpretation of the SAXS signal that will be relevant for future work under environmentally relevant conditions.

Published
2022

12. Why local and non-local terms are essential for second harmonic generation simulation?

Author

Yann Foucaud, Jean-François Dufrêche, Bertrand Siboulet, Magali Duvail, Alban Jonchère, Olivier Diat, Rodolphe Vuilleumier, Modélisation Mésoscopique et Chimie Théorique (LMCT), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Ions aux Interfaces Actives (L2IA), Processus d'Activation Sélective par Transfert d'Energie Uni-électronique ou Radiatif (UMR 8640) (PASTEUR), Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Physics::Optics, General Physics and Astronomy, Physical and Theoretical Chemistry
Abstract

International audience; Second Harmonic Generation (SHG) today represents one of the most powerful techniques to selectively probe all types of interfaces. However, the origin of the SHG signal at a molecular level is still debated since the local dipole contribution, which is strongly correlated to the molecular orientation can be counterbalanced by non-local quadrupole contributions. Here, we propose a method to simulate the SHG signal of a model water/air interface from the molecular response of each contribution. This method includes both local and non-local terms, which are represented, respectively, by the dependency of the polarisability and hyperpolarisability upon the chemical environment of the molecule and by the bulk quadrupole response. The importance of both terms for the sound simulation of the SHG signals and their interpretation is assessed. We demonstrate that the sole dipole term is unable to simulate a SHG signal, even if the dependency of the hyperpolarisability on the local environment is considered. The inclusion of the bulk quadrupole contribution, which largely dominates the dipole contribution, is essential to predict the SHG response, although the accuracy of the prediction is increased when the dependency upon the local environment is considered.

Published
2022

13. Impact of complex irradiation scenarios on the structure and the properties of the International Simple Glass

Author

C. Gillet, S. Szenknect, M. Tribet, S. Miro, T. Charpentier, M. Odorico, S. Peuget, Département de recherche sur les Procédés et Matériaux pour les Environnements complexes (DPME), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Interfaces de Matériaux en Evolution (LIME), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Laboratoire Structure et Dynamique par Résonance Magnétique (LCF) (LSDRM), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Etude de la Matière en Mode Environnemental (L2ME), and This work was performed in the framework of the Vestale project co-funded by EDF, CEA and Orano

Subjects
Nuclear and High Energy Physics, MESH: Structure, MESH: ISG glass, Nuclear Energy and Engineering, MESH: Macroscopic properties, MESH: External irradiation, General Materials Science, [CHIM.MATE]Chemical Sciences/Material chemistry
Abstract

International audience; This study addresses the consequences of three irradiation scenarios on the structure and macroscopic properties of the ISG glass. The coupling effect between 2.5 MeV electron irradiation (simulating the effects of beta particles and gamma rays) and 7 MeV Au irradiation (simulating the nuclear collisions of the recoil nuclei of alpha decays) was studied by comparing two monobeam irradiations with a sequential double beam irradiation. Various experimental techniques were used to characterize the glass structure and properties, combining Raman, NMR, IR-ATR spectroscopies, hydrostatic weighing, He pycnometry, X-Ray Reflectivity, AFM, surface tension and Vickers microhardness measurements. Electron irradiation up to 3.25 GGy induces only small changes of ISG glass structure and macroscopic properties than Au irradiation. Moreover, the magnitude of the changes induced by the sequential irradiation scenario, i.e. electron followed by Au ions, are the same as the one induced by the monobeam irradiation by Au ions, except for the surface tension. Because the bulk damage state are similar, this work demonstrates that there is no coupling between the damage generated by the electron irradiation and the subsequent nuclear collision generated by Au ions. Finally, the hardness and density changes of ISG glass are very similar to those of SON68 glass when submitted to similar irradiation conditions by electron or nuclear collisions. Therefore ISG glass is found to be a good glass surrogate with respect to radiation ageing of the SON68 glass.

Published
2022

14. First observation of [Pu6(OH)4O4 ]12+ cluster during the hydrolytic formation of PuO2 nanoparticles using H/D kinetic isotope effect

Author

Manon Cot-Auriol, Matthieu Virot, Thomas Dumas, Olivier Diat, Denis Menut, Philippe Moisy, Sergey I. Nikitenko, Sonochimie dans les Fluides Complexes (LSFC), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Institut des Sciences et technologies pour une Economie Circulaire des énergies bas carbone (ISEC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Ions aux Interfaces Actives (L2IA), Synchrotron SOLEIL (SSOLEIL), and Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials Chemistry, Metals and Alloys, Ceramics and Composites, General Chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, [CHIM.RADIO]Chemical Sciences/Radiochemistry, Catalysis, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials
Abstract

New insights are provided about the formation mechanism of PuO2 nanoparticles (NPs) by investigating an unprecedented kinetic isotope effect observed during their hydrolytic synthesis in H2O or D2O media.

Published
2022

15. Synthesis and multi-scale properties of PuO2 nanoparticles: recent advances and open questions

Author

Matthieu Virot, Thomas Dumas, Manon Cot-Auriol, Philippe Moisy, Sergey I. Nikitenko, Sonochimie dans les Fluides Complexes (LSFC), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Institut des Sciences et technologies pour une Economie Circulaire des énergies bas carbone (ISEC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)

Subjects
General Engineering, General Materials Science, Bioengineering, General Chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, [CHIM.RADIO]Chemical Sciences/Radiochemistry, Atomic and Molecular Physics, and Optics
Abstract

The review focuses on the recent relevant progresses observed about PuO2 nanoparticle syntheses and characterizations including the recently deciphered electronic, structural and physico-chemical properties.

Published
2022

16. Isotopic effect on the formation kinetics of Pu(IV) intrinsic colloids

Author

Cot Auriol, Manon, Virot, Matthieu, Dumas, Thomas, Diat, Olivier, Menut, Denis, Moisy, Philippe, Nikitenko, Sergey I., Sonochimie dans les Fluides Complexes (LSFC), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Institut des Sciences et technologies pour une Economie Circulaire des énergies bas carbone (ISEC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), and Ions aux Interfaces Actives (L2IA)

Subjects
[CHIM.MATE]Chemical Sciences/Material chemistry
Abstract

International audience

Published
2022

17. Sonoluminescence Spectra in the First Tens of Seconds of Sonolysis of [BEPip][NTf2], at 20 kHz under Ar

Author

Rachel Pflieger, Manuel Lejeune, Micheline Draye, Sonochimie dans les Fluides Complexes (LSFC), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Environnements, Dynamiques et Territoires de Montagne (EDYTEM), and Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)

Subjects
sonolysis, degradation, ionic liquid, viscosity, sonoluminescence, Chemistry (miscellaneous), Organic Chemistry, Drug Discovery, Molecular Medicine, Pharmaceutical Science, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Physical and Theoretical Chemistry, Analytical Chemistry
Abstract

Following recent works on the sonochemical degradation of butyl ethyl piperidinium bis-(trifluoromethylsulfonyl)imide ([BEPip][NTf2]), monitoring of sonoluminescence (SL) spectra in the first tens of seconds of sonolysis was needed to better characterize the formed plasma and to question the correlation of the SL spectra with the viscosity. A very dry [BEPip][NTf2] ionic liquid (IL) and a water-saturated liquid are studied in this paper. In both cases, IL degradation is observed as soon as SL emission appears. It is confirmed that the initial evolution of the SL intensity is closely linked to the liquid viscosity that impacts the number of bubbles; however, other parameters can also play a role, such as the presence of water. The water-saturated IL shows more intense SL and faster degradation. In addition to the expected bands, new emission bands are detected and attributed to the S2 B-X emission, which is favored in the water-saturated ionic liquid.

Published
2022
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18. Individual adsorption of low volatility pheromones: Amphiphilic molecules on a clean water–air interface

Author

Jean-François Dufrêche, Ludovic Jami, Thomas ZEMB, Jerome Casas, Institut de recherche sur la biologie de l'insecte UMR7261 (IRBI), Université de Tours (UT)-Centre National de la Recherche Scientifique (CNRS), Modélisation Mésoscopique et Chimie Théorique (LMCT), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), and ANR-18-CE29-0010,MULTISEPAR,Modelisation multi-échelle des phases organiques pour l'extraction liquid-liquide(2018)

Subjects
Aerosols, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, General Physics and Astronomy, Thermodynamics, Water, Adsorption, Physical and Theoretical Chemistry, Pheromones
Abstract

Environmental conditions can alter olfactory scent and chemical communication among biological species. In particular, odorant molecules interact with aerosols. Thermodynamics variables governing the adsorption from air to water surface of bombykol, the most studied pheromone, and of three derivative molecules, bombykal, bombykoic acid, and bombykyle acetate, are computed by steered and un-biased molecular dynamics in order to compare the role of their polar head group on adsorption on aqueous aerosols. When adsorbed, the molecule center of mass stands at about 1.2 Å from the interface and oscillates on the same length scale, trapped in an energy well. Gibbs energy of adsorption and desorption time of bombykol are found to be 9.2 kB T and 59 µs, respectively. The following ordering between the molecules is observed, reading from the more to the least adsorbed: bombykoic acid [Formula: see text] bombykol [Formula: see text] bombykoic acetate [Formula: see text] bombykal. It originates from a complex interplay of entropy and enthalpy. The entropy and enthalpy of adsorption are discussed in the light of structural arrangement, H-bonding, and hydrophilic tail positioning of the molecules at the interface. Our results show that, when dispersed in the air, pheromones adsorb on aqueous aerosols. However, the individual residence time is quite short on pure water surfaces. Aerosols can, therefore, only have a decisive influence on chemical communication through collective effects or through their chemical composition that is generally more complex than that of a pure water surface.

Published
2022

19. Apport des ultrasons de puissance pour la préparation de nanoparticules colloïdales de UO2+x

Author

Cot Auriol, Manon, Virot, Matthieu, Dumas, Thomas, Moisy, Philippe, Nikitenko, Sergey I., Sonochimie dans les Fluides Complexes (LSFC), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Institut des Sciences et technologies pour une Economie Circulaire des énergies bas carbone (ISEC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)

Subjects
[CHIM.MATE]Chemical Sciences/Material chemistry
Abstract

International audience

Published
2022

20. Effet isotopique cinétique et formation de nanoparticules colloïdales de PuO2

Author

Cot Auriol, Manon, Virot, Matthieu, Dumas, Thomas, Diat, Olivier, Menut, Denis, Moisy, Philippe, Nikitenko, Sergey I., Sonochimie dans les Fluides Complexes (LSFC), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Laboratory of Interactions Ligand-Actinide (LILA), Département de recherche sur les procédés pour la mine et le recyclage du combustible (DMRC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Ions aux Interfaces Actives (L2IA), and Institut des Sciences et technologies pour une Economie Circulaire des énergies bas carbone (ISEC)

Subjects
[CHIM.MATE]Chemical Sciences/Material chemistry
Abstract

International audience

Published
2022

21. Deciphering the reaction mechanisms of photothermal hydrogen production using H/D kinetic isotope effect

Author

Sara El Hakim, Tony Chave, Sergey I. Nikitenko, Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Sonochimie dans les Fluides Complexes (LSFC), and Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)

Subjects
[CHIM.CATA]Chemical Sciences/Catalysis, Catalysis
Abstract

International audience; H/D kinetic isotope effect has been employed to study the mechanism of the thermally assisted photocatalytic hydrogen production over noble metal-free Ti@TiO$_2$ core–shell nanoparticles. We have found that the observed large H/D isotope separation factor (αH = 11.3 ± 1.7–6.2 ± 0.9) is due to the electron hole-mediated cleavage of OH bond. It was concluded that strong H/D isotopic selectivity is associated with significant photothermal effect.

Published
2022

22. Sonochemistry of actinides: from ions to nanoparticles and beyond

Author

Sergey I. Nikitenko, Matthieu Virot, Philippe Moisy, Sonochimie dans les Fluides Complexes (LSFC), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Institut des Sciences et technologies pour une Economie Circulaire des énergies bas carbone (ISEC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)

Subjects
[CHIM]Chemical Sciences, Physical and Theoretical Chemistry, [CHIM.RADIO]Chemical Sciences/Radiochemistry
Abstract

Sonochemistry studies chemical and physical effects in liquids submitted to power ultrasound. These effects arise not from a direct interaction of molecules with sound waves, but rather from the acoustic cavitation: the nucleation, growth, and implosive collapse of microbubbles in liquids submitted to power ultrasound. The violent implosion of bubbles leads to the formation of chemically reactive species. In principle, each cavitation bubble can be considered as a microreactor initiating chemical reactions at mild conditions. In addition, microjets and shock waves accompanied bubble collapse produce fragmentation, dispersion and erosion of solid surfaces or particles. Microbubbles oscillating in liquids also enable nucleation and precipitation of nanosized actinide compounds with specific morphology. This review focuses on the versatile sonochemical processes with actinide ions and particles in homogenous solutions and heterogenous systems. The redox reactions in aqueous solutions, dissolution or precipitation of refractory solids, synthesis of actinide nanoparticles, and ultrasonically driving decontamination are considered. The guideline for further research is also discussed.

Published
2022

23. ElectroLeaching-ElectroChemical Deposition (EL-ECD) of gold and palladium in a deep eutectic solvent (DES)

Author

Benoit Villemejeanne, Sophie Legeai, Eric Meux, Sandrine Dourdain, Hakima Mendil-Jakani, Emmanuel Billy, ARC-Nucleart CEA Grenoble (NUCLEART), Laboratoire d'Innovation pour les Technologies des Energies Nouvelles et les nanomatériaux (LITEN), Institut National de L'Energie Solaire (INES), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Institut National de L'Energie Solaire (INES), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS), Institut Jean Lamour (IJL), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), ANR, and ANR-20-CE08-0035,EE4Precious,Electrolixiviation-Electrodepôt pour la valorisation des métaux précieux contenus dans les déchets d'équipements électroniques/électroniques(2020)

Subjects
Process Chemistry and Technology, Deep eutectic solvents, [SDE]Environmental Sciences, Electrochemistry, Chemical Engineering (miscellaneous), [CHIM]Chemical Sciences, [CHIM.MATE]Chemical Sciences/Material chemistry, Pollution, Waste Management and Disposal, Precious metals recovery
Abstract

International audience; Precious metal refining from ore or electronic devices includes hydrometallurgical processes with major concern about toxicity or wastewater production. As an alternative, one-step electroleaching-electrochemical deposition process (EL-ECD) using ionic liquid mixtures was evaluated for palladium and gold recovery. A halide based ionic liquid combined with a diluting ionic liquid was chosen among ten electrolytes after cyclic voltammetry and potentiostatic experiments. These low viscous electrolytes allow complexing Au and Pd, leading to metal leaching at low anodic potential. Moreover, the complexes formed could be simultaneously deposited at the cathode. Metal behaviour is similar for all halide anions tested (chloride, bromide and iodide). Results show that chloride based mixtures are the more suitable electrolyte providing the highest leaching faradic yield. This process appears more sustainable than conventional processes (chlorination, cyanide leaching) thanks to the electrolyte stability limiting solvent losses but also workers exposition.

Published
2022

24. Impact of ruthenium metallic particles on the dissolution of UO2 in nitric acid

Author

Thibault Kaczmarek, Stéphanie Szenknect, Laurent Claparède, Martiane Cabié, Xavier Le Goff, Adel Mesbah, Renaud Podor, Nicolas Dacheux, Interfaces de Matériaux en Evolution (LIME), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Centre Pluridisciplinaire de Microscopie Electronique et de Microanalyse (AMU CP2M), Aix Marseille Université (AMU), and Etude de la Matière en Mode Environnemental (L2ME)

Subjects
Chemistry (miscellaneous), Materials Science (miscellaneous), Materials Chemistry, Ceramics and Composites, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, [CHIM.RADIO]Chemical Sciences/Radiochemistry
Abstract

UO2 pellets incorporating 3 mol.% of Ru was prepared by using a wet chemistry route and then characterised. The speciation, morphology, as well as spatial distribution of Ru in the sintered samples, were determined. The synthesised samples were submitted to dissolution tests in 0.1 M nitric acid at 60 °C and the dissolution of pure UO2 pellets was also studied with and without the presence of Ru metallic particles in the solution. The evolution of the U, Ru, and nitrous acid concentrations in solution was measured and the residues of dissolution were further characterised. The obtained results unambiguously demonstrated the catalytic activity of Ru-metal particles during UO2 dissolution in nitric acid provided that a solid/solid interface existed between UO2 and Ru-metal particles. This positive impact on the dissolution kinetics of UO2 was supported by redox reactions taking place at both nitric acid solution/Ru-metal particles and at Ru-metal particles/UO2 interfaces.

Published
2022

25. Long-Range Organization Study of Piperidinium-Based Ionic Liquids by Polarizable Molecular Dynamics Simulations

Author

Sébastien Le Crom, Sandrine Dourdain, Stéphane Pellet-Rostaing, Magali Duvail, Modélisation Mésoscopique et Chimie Théorique (LMCT), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), and ANR-16-IDEX-0006,MUSE,MUSE(2016)

Subjects
Condensed Matter::Soft Condensed Matter, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Anions, Cations, Physics::Atomic and Molecular Clusters, Materials Chemistry, Ionic Liquids, Physics::Chemical Physics, Physical and Theoretical Chemistry, Molecular Dynamics Simulation, Imides, Surfaces, Coatings and Films
Abstract

International audience; The nanoscale organization of some classes of ionic liquids is responsible for their singular properties. In this paper, we use polarizable molecular dynamics simulations and small-angle X-ray scattering to probe the structure of two piperidinium- and (trifluoromethylsulfonyl)imide-based ionic liquids ([EBPip$^+$][NTf$_2^–$] and [EOPip$^+$][NTf$_2^–$]) that differ in the alkyl chain length of their cation. The X-ray scattering intensities calculated numerically, from the radial distribution functions, are in excellent agreement with the experimental data. The analysis of the different contributions of the X-ray scattering data allowed us to highlight the correlations responsible for the low q peak observed for the long-chain alkyl cations. New angular analyses showed that anions were more likely to align with alkyl chains as their size increased, inducing angular correlation between anions at larger distances. They also showed that the long alkyl chains of the cations aligned more with each other than the short ones. These more aligned alkyl chains induce a smaller volume of the apolar microdomains compared to the well-studied imidazolium-based ionic liquids, leading to the smaller correlation distance for piperidinium-based ionic liquids.

Published
2022

26. Modélisation multi-échelle de solutions organiques et systèmes interfaciaux pour l’extraction liquide-liquide

Author

Vatin, Marin, Modélisation Mésoscopique et Chimie Théorique (LMCT), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Université de Montpellier, Jean-François Dufrêche, Philippe Guilbaud, and STAR, ABES

Subjects
Separative chemistry, [CHIM.OTHE] Chemical Sciences/Other, Dynamique moléculaire, Chimie séparative, Thermodynamics, Molecular dynamics, [CHIM.OTHE]Chemical Sciences/Other, Thermodynamique
Abstract

This thesis presents a set of models and methods for the structural and thermodynamic description of organic solutions and interfacial systems encountered in the context of liquid-liquid extraction. The models and methods are based on an approach that is essentially molecular. It has a strong numerical component. A study based on a molecular dynamics approach was used to investigate the phase separation of a water-oil mixture. It has also been used to simulate organic solutions whose supramolecular organization has been verified by comparisons between the experimental and the molecular simulations signals associated with small angle X-ray scattering. The supramolecular organization has been characterized more finely during studies devoted to the aggregation in organic phase in the presence of extractant malonamide molecules (DMDOHEMA) and of europium nitrate salts thanks to advanced numerical treatments presented in this thesis. These numerical treatments allowed the calculation of the mean distributions of the chemical species formed in the organic solutions. From these distributions, thermodynamic models of the aggregation phenomena in the organic phase based on numerical and analytical approaches have been developed. These models allowed the calculation of the energies of formation of the species in solution according to their composition, and the determination of the mean aggregation numbers in very good agreement with the experimental data, the study of the mechanisms associated with the phenomenon of “third phase formation” thanks to a super-species percolation model and the calculation of quantities associated with the kinetics of formation of aggregates in organic phase, Cette thèse présente un ensemble de modèles et de méthodes pour la description structurale et thermodynamique des solutions organiques et des systèmes interfaciaux rencontrées dans le contexte de l’extraction liquide-liquide. Les modèles et méthodes sont basés sur une approche qui est essentiellement à l’échelle moléculaire et ont une forte composante numérique. Une étude basée sur une approche par dynamique moléculaire a été utilisée afin d’étudier la séparation de phase d’un mélange eau-huile. Elle a aussi été utilisée afin de simuler les solutions organiques dont l’organisation supramoléculaire a été vérifiée par des comparaisons entre les spectres de diffusions des rayons X aux petits angles expérimentaux et issus de ces simulations moléculaires. L’organisation supramoléculaire a pu être caractérisée plus finement au cours d’études consacrées à l’agrégation en phase organique en présence de molécules extractantes de type malonamide (DMDOHEMA) et de sels de nitrate d’europium grâce à des traitements numériques poussés présentés dans cette thèse ; notamment par le calcul des distributions moyennes des espèces chimiques formées dans les solutions organiques. A partir de ces distributions, des modèles thermodynamiques des phénomènes d’agrégation en phase organique basés sur des approches numériques et analytiques ont été élaborés. Ces modèles ont notamment permis de calculer les énergies de formation des espèces en solution en fonction de leur composition, des nombres d’agrégation moyen en très bon accord avec les données expérimentales, d’étudier les mécanismes associés au phénomène de « formation de la troisième phase » par un modèle de percolation et l’étude de super-espèces et enfin, de calculer des grandeurs associées à la cinétique de formations des agrégats en phase organique.

Published
2022

27. Effect of alkyl chain configuration of tertiary amines on uranium extraction and phase stability – Part I: Evaluation of phase stability, extraction, and aggregation properties

Author

Zijun Lu, Sandrine Dourdain, Bruno Demé, Jean-François Dufrêche, Thomas Zemb, Stéphane Pellet-Rostaing, Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Institut Laue-Langevin (ILL), and Modélisation Mésoscopique et Chimie Théorique (LMCT)

Subjects
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Materials Chemistry, Physical and Theoretical Chemistry, Condensed Matter Physics, Spectroscopy, Atomic and Molecular Physics, and Optics, Electronic, Optical and Magnetic Materials
Abstract

International audience; Amine-based extraction processes are broadly exploited for the selective extraction of uranium from sulfuric leaching liquors. The molecular forces (that is, the enthalpy associated with the multi-scale structuration of tertiary amines) are balanced by entropic effects that have not yet been identified. This first part in a series of reports describes the effects of the alkyl chain configuration on the phase stability and aggregation properties of tertiary amines. It is demonstrated that tertiary amines with longer or slightly branched alkyl chains provide better phase stability and enable constant extraction of uranium. In comparison, more branching of the alkyl chains hinders the formation of a highly curved interfacial layer, thus preventing efficient extraction. Combined small-angle scattering determination of the nanostructures in the organic phase and oil–water surface tension measurements revealed that the alkyl chains effects on the efficiency of the extraction process and phase stability are associated with reverse aggregates with smaller polar core volumes and less co-extracted water, suggesting that packing of the alkyl chains has a direct impact on the extraction efficiency of the solvent extraction system.

Published
2022

28. 3D-Printing of porous materials: Application to Metal-Organic Frameworks

Author

David Pianca, Michaël Carboni, Daniel Meyer, Systèmes HYbrides pour la Séparation (LHyS), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), and Université de Montpellier (UM)

Subjects
Mechanics of Materials, Mechanical Engineering, General Materials Science, [CHIM.MATE]Chemical Sciences/Material chemistry, Condensed Matter Physics, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2022

29. Sonoluminescence emission spectra of a 3.6 MHz HIFU in sweeping mode

Author

Noura, Sleiman, Loïc, Hallez, Rachel, Pflieger, Sergey I, Nikitenko, Jean-Yves, Hihn, Univers, Transport, Interfaces, Nanostructures, Atmosphère et environnement, Molécules (UMR 6213) (UTINAM), Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université de Franche-Comté (UFC), Université Bourgogne Franche-Comté [COMUE] (UBFC)-Université Bourgogne Franche-Comté [COMUE] (UBFC), Institut de recherche technologique Matériaux Métallurgie et Procédés (IRT M2P), Sonochimie dans les Fluides Complexes (LSFC), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), and Université de Montpellier (UM)

Subjects
Cavitation, Acoustics and Ultrasonics, Organic Chemistry, Acoustics. Sound, QC221-246, Emission spectra, Acoustics, HIFU, Inorganic Chemistry, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Chemistry, High-Intensity Focused Ultrasound Ablation, Chemical Engineering (miscellaneous), Environmental Chemistry, Sonoluminescence, Radiology, Nuclear Medicine and imaging, Frequency sweep, QD1-999, ComputingMilieux_MISCELLANEOUS
Abstract

Use of sweeping mode with a 3.6 MHz High Intensity Focused Ultrasound (HIFU) allows cavitation activity to be controlled. This is especially true in the pre-focal zone where the high concentration of bubbles acts as an acoustic reflector and quenches cavitation above this area. Previous studies attributed the enhancement of cavitation activity under negative sweep to the activation of more bubble nuclei, requiring deeper investigations. After mapping this activity with SCL measurements, cavitation noise spectra were recorded. The behavior of the acoustic broadband noise follows the sonochemical one i.e., showing the same attenuation (positive scan) or intensification (negative scan) of cavitational activity. In 1 M NaCl 3.7 mM 2-propanol solution saturated by a mixture of Ar-15.5%O2-2.2%N2, intensities of SL spectra are high enough to allow detection of several molecular emissions (OH, NH, C2, Na) under negative frequency sweeps. This is the first report of molecular emissions at such high frequency. Their intensities are low, and they are very broad, following the trend obtained at fixed frequency up to 1 MHz. Under optimized conditions, CN emission chosen as a spectroscopic probe is strong enough to be simulated, which is reported for the first time at such high frequency. The resulting characteristics of the plasma do not show any spectral difference, so bubble nature is the same in the pre-and post-focal zone under different sweeping parameters. Consequently, SL and SCL intensification was not related to a change in plasma nature inside the bubbles but to the number of cavitation bubbles.

Published
2022

30. Real-Time Capturing of Microscale Events Controlling the Sintering of Lead-Free Piezoelectric Potassium-Sodium Niobate

Author

Micka Bah, Renaud Podor, Richard Retoux, Fabian Delorme, Kevin Nadaud, Fabien Giovannelli, Isabelle Monot‐Laffez, André Ayral, GREMAN (matériaux, microélectronique, acoustique et nanotechnologies) (GREMAN - UMR 7347), Université de Tours (UT)-Institut National des Sciences Appliquées - Centre Val de Loire (INSA CVL), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Etude de la Matière en Mode Environnemental (L2ME), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Laboratoire de cristallographie et sciences des matériaux (CRISMAT), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Institut Européen des membranes (IEM), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)

Subjects
Biomaterials, Dielectric responses, General Materials Science, Pore stability, General Chemistry, Matter transport mechanisms, Grain-boundary energy, [CHIM.MATE]Chemical Sciences/Material chemistry, In situ sintering, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Lead-free ceramics, Biotechnology, Grain growth
Abstract

International audience; Sintering is a very important process in materials science and technological applications. Despite breakthroughs in achieving optimized piezoelectric properties, fundamentals of K$_{0.5}$Na$_{0.5}$NbO$_3$ (KNN) sintering are not yet fully understood, facing densification versus grain growth competition. At present, microscale events during KNN sintering under reducing atmospheres are real-time monitored using a High Temperature-Environmental Scanning Electron Microscope. A two contacting KNN particles model satisfying the Kingery and Berg's bulk diffusion model is reported. Dynamic events like individual grain growth and grain elimination process are explored through a postanalysis of recorded image series. The diffusion coefficient for oxygen vacancies of 10$^{−8}$ cm$^2$ s$^{−1}$ and average boundary mobility of 10$^{−9}$ cm$^4$ J$^{−1}$ s$^{−1}$ are reported for the KNN ceramics. Moreover, the local pore shrinkage is consistent with the Kingery and François's concept of pore stability except that pore curvatures are not all concave, convex or flat due to anisotropic grain-boundary energies. The global grain growth kinetics are described using parabolic and/or cubic laws. The effect of atmospheres and microstructure evolution on the intrinsic and extrinsic contributions to the dielectric response using Rayleigh's law is also explored. These results bring a new breath for KNN sintering studies in order to adapt the sintering process.

Published
2022

31. Terephthalaldehyde–Phenolic Resins as a Solid-Phase Extraction System for the Recovery of Rare-Earth Elements

Author

Ruth Oye Auke, Guilhem Arrachart, Romain Tavernier, Ghislain David, Stéphane Pellet-Rostaing, Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)

Subjects
solid-phase extraction, terephthalaldehyde, ion exchange, rare-earth elements, Solid-phase extraction, QD241-441, Polymers and Plastics, Organic chemistry, [CHIM]Chemical Sciences, General Chemistry, Terephthalaldehyde, Rare-earth elements, Article, Ion exchange
Abstract

International audience; Rare-earth elements (REEs) are involved in most high technology devices and have become critical for many countries. The progress of processes for the extraction and recovery of REEs is therefore essential. Liquid–solid extraction methods are an attractive alternative to the conventional solvent extraction process used for the separation and/or purification of REEs. For this purpose, a solid-phase extraction system was investigated for the extraction and valorization of REEs. Ion-exchange resins were synthesized involving the condensation of terephthalaldehyde with resorcinol under alkaline conditions. The terephthalaldehyde, which is a non-hazardous aromatic dialdehyde, was used as an alternative to formaldehyde that is toxic and traditionally involved to prepare phenolic ion-exchange resins. The resulting formaldehyde-free resole-type phenolic resins were characterized and their ion-exchange capacity was investigated in regard to the extraction of rare-earth elements. We herein present a promising formaldehyde and phenol-free as a potential candidate for solid–liquid extraction REE with a capacity higher than 50 mg/g and the possibility to back-extract the REEs by a striping step using a 2 M HNO3 solution.

Published
2022

32. On interactions in binary mixtures used in solvent extraction: Insights from combined Isothermal Titration Calorimetry experiments and Molecular Dynamics simulations

Author

Nathalie Boubals, Jean-François Dufrêche, Marie-Christine Charbonnel, Mathilde Coquil, Magali Duvail, Laboratory of Interactions Ligand-Actinide (LILA), Département de recherche sur les procédés pour la mine et le recyclage du combustible (DMRC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Modélisation Mésoscopique et Chimie Théorique (LMCT), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), and Université de Montpellier (UM)

Subjects
Materials science, Enthalpy, Binary mixtures, Thermodynamics, 02 engineering and technology, Calorimetry, Molecular dynamics, 010402 general chemistry, 01 natural sciences, Diluent, Materials Chemistry, Physical and Theoretical Chemistry, Spectroscopy, Alkyl, Complex fluid, chemistry.chemical_classification, Isothermal titration calorimetry, Dilution, Isothermal titration calorimetry (ITC), 021001 nanoscience & nanotechnology, Condensed Matter Physics, Atomic and Molecular Physics, and Optics, 0104 chemical sciences, Electronic, Optical and Magnetic Materials, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry, Solution thermodynamics, 0210 nano-technology
Abstract

International audience; Despite its importance, the description of liquid–liquid extraction is made difficult because the link between the experimental methods and the interactions present in the solution is not direct due to the many organisation phenomena that can occur. We propose a new methodology combining microcalorimetric measurements and molecular modelling to better describe the nature and strength of these interactions in these complex fluids by focusing on extractant-diluent mixtures (N,N-dialkylamides + n-alkanes). Enthalpies of dilution were obtained by microcalorimetric measurements at 298 K for each n-dodecane and n-heptane with DEHiBA and for n-dodecane with DEHBA. These results have been compared, thanks to a new method that we present here, to molecular dynamics simulations carried out on these same systems. We especially analyzed the influence of the alkyl branching of the extracting molecules and the role of the diluent. Globally, the excess enthalpy is such that these mixtures are energetically not very different from regular solutions but the detailed balance shows an important attraction between the extractants, which can lead to the formation of macromolecular entities favouring extraction. Calorimetry appears to be a method of choice for linking experiments and molecular modelling in these complex liquid mixtures, and experimental developments could benefit from using it more often, especially to validate force-fields.

Published
2022

33. Effect of ruthenium metallic particles on the kinetics of dissolution of UO2 in nitric acid

Author

Kaczmarek, Thibault, Szenknect, Stephanie, Claparede, Laurent, Cabie, Martiane, Le Goff, Xavier, Mesbah, Adel, Podor, Renaud, Dacheux, Nicolas, Interfaces de Matériaux en Evolution (LIME), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Centre Pluridisciplinaire de Microscopie Electronique et de Microanalyse (AMU CP2M), Aix Marseille Université (AMU), and Etude de la Matière en Mode Environnemental (L2ME)

Subjects
[CHIM.INOR]Chemical Sciences/Inorganic chemistry
Abstract

International audience; UO2 pellets containing 3 mol. % of Ru were prepared then characterized. The speciation, the morphology and the spatial distribution of Ru in the sintered samples were determined. These samples were submitted to dissolution tests in nitric and hydrochloric acids, as well as UO2 pellets in the presence and in absence of Ru-metal particles in solution. The evolution of the elemental concentrations in solution was followed, then the residues of dissolution were characterized. The presence of metallic particles of Ru incorporated in the pellet increased significantly the dissolution rate of UO2, both in nitric and hydrochloric media. A mechanism was then proposed to explain their influence on the kinetics of dissolution of UO2 in nitric acid solutions.

Published
2022

34. Desorption of Cs from vermiculite by ultrasound assisted ion exchange

Author

Sophie Herr, Antoine Leybros, Yves Barre, Sergueï Nikitenko, Rachel Pflieger, Sonochimie dans les Fluides Complexes (LSFC), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Département de recherche sur les procédés pour la mine et le recyclage du combustible (DMRC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)

Subjects
Environmental Engineering, Health, Toxicology and Mutagenesis, Public Health, Environmental and Occupational Health, Cesium, General Medicine, General Chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Pollution, [SDE.ES]Environmental Sciences/Environmental and Society, Ion Exchange, Soil, Cesium Radioisotopes, Soil Pollutants, Radioactive, Environmental Chemistry, Aluminum Silicates, Adsorption, ComputingMilieux_MISCELLANEOUS
Abstract

Nuclear power plant accidents typically lead to the contamination of large volumes of soils with radioactive cesium. This element is hard to desorb from soil, especially when it is bound to mica minerals, and aggressive and energy-consuming techniques are often required. In this study, we investigated the use of ultrasound with Mg

Published
2022

35. Simultaneous H/D and $^{13}$C/$^{12}$C anomalous kinetic isotope effects during the sonolysis of water in the presence of carbon monoxide

Author

Sergey I. Nikitenko, Tony Chave, Matthieu Virot, Rachel Pflieger, Sonochimie dans les Fluides Complexes (LSFC), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), and Université de Montpellier (UM)

Subjects
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [PHYS.PHYS.PHYS-PLASM-PH]Physics [physics]/Physics [physics]/Plasma Physics [physics.plasm-ph], General Materials Science, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Physical and Theoretical Chemistry
Abstract

International audience; Splitting of water molecules driven by ultrasound plays a central role in sonochemistry. While studies of sonoluminescence revealed the formation of a plasma inside the cavitation bubble, much less is known about the contribution of plasma chemical processes to the sonochemical mechanisms. Herein, we report for the first time sonochemical processes in water saturated with pure CO. The presence of CO causes a large increase in the H/D kinetic isotope effect (KIE) to $\alpha_H$ = 14.6 ± 1.8 in a 10% H$_2$O/D$_2$O mixture under 20 kHz ultrasound.The anomalous H/D KIE is attributed to electron quantum tunneling in the plasma produced by cavitation. In addition, CO$_2$ formed simultaneously with hydrogen during the sonochemical process is enriched with the $^{13C}$C isotope, which indicates a VV pumping mechanism typical for non-equilibrium plasma. Both observed KIEs unambiguously point to the contribution of quantum effects in sonochemical mechanisms.

Published
2022

36. How acidity rules synergism and antagonism in liquid–liquid extraction by lipophilic extractants — Part II: application of the ienaic modelling

Author

Stéphane Pellet-Rostaing, Sandrine Dourdain, J. Rey, Klemen Bohinc, Mario Špadina, Jean-François Dufrêche, Thomas Zemb, Modélisation Mésoscopique et Chimie Théorique (LMCT), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), University of Ljubljana, Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), ANR-18-CE29-0010,MULTISEPAR,Modelisation multi-échelle des phases organiques pour l'extraction liquid-liquide(2018), ANR-10-LABX-0005,CheMISyst,CHEmistry of Molecular and Interfacial Systems(2010), European Project: 320915,EC:FP7:ERC,ERC-2012-ADG_20120216,REE-CYCLE(2013), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), and Faculty of Health Sciences, University of Ljubljana

Subjects
solvent extraction, colloidal model, extraction landscape, polydispersity, aggregtaion, Chemistry, General Chemical Engineering, Inorganic chemistry, droplet model, synergy, 02 engineering and technology, General Chemistry, 010403 inorganic & nuclear chemistry, 01 natural sciences, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, 020401 chemical engineering, Liquid–liquid extraction, ienaics, 0204 chemical engineering, Solvent extraction, Antagonism, polydispersity in aggregation
Abstract

International audience; In this article Part II, we consider the application of ienaic modeling for solvent extraction of rare earths in the case of the mixed DMDOHEMA/HDEHP extractant system. The system exhibits a synergistic extraction effect depending on the acid concentration and the extractant mole fraction, as demonstrated in the experimental article Part I. In this work, we directly compare experimental findings with theoretical predictions of the droplet model. The model considers the effective free energy of transfer as a combination of competing molecular forces, but contrary to previous micelle models that focus only on the dominant stoichiometry, it allows calculations of free energies of every possible spherical aggregate. The resulting image of the extraction process is that different behaviors can be obtained depending on the acidity and mole fraction of extractants, which are associated with different aggregation regimes in a complex free energy landscape of the system. Nevertheless, self-assembly is tuned by the extraction of all solutes, and not only the target metal cations.

Published
2022

37. Generating metal-organic frameworks (MOFs) from photovoltaic modules for wastewater remediation

Author

Huu Khue Pham, Ying Sim, Michaël Carboni, Daniel Meyer, Nripan Mathews, School of Materials Science and Engineering, Energy Research Institute @ NTU (ERI@N), Singapore-CEA Alliance for Research in Circular Economy (SCARCE), Nanayang Technological University (NTU), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Energy Research Institute @ NTU (ERI@N), Nanyang Technological University [Singapour]-Nanyang Technological University [Singapour], Systèmes HYbrides pour la Séparation (LHyS), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), and This research/project is supported by the National Research Foundation, Singapore, and National Environment Agency, Singapore underits Closing the Waste Loop Funding Initiative (Award No. USS-IF2018–4).

Subjects
Materials [Engineering], Process Chemistry and Technology, Upcycling, Solar Panel, Chemical Engineering (miscellaneous), Recycling, [CHIM.MATE]Chemical Sciences/Material chemistry, Pollution, Waste Management and Disposal, Wastewater Remediation, Metal-Organic Framework
Abstract

Upcycling enables the recycling efforts of E-waste to be more feasible and economically viable. Photovoltaic (PV) energy adoption has increased drastically over the years and is expected to become a mainstream energy source for the future due to its sustainability. However, waste management remains a problem as the PV panels gradually reach their end-of-life and start piling up. Many recycling strategies have been executed, but upcycling efforts to form high-value products from these PV panels are underexplored. In this paper, we report three different synthetic routes to generate metal-organic framework (MOF), MIL-53(Al) (Matériaux de l′Institut Lavoisier (MIL)), with the polymeric backsheet and aluminum that can be derived from solar panels. The synthesized MOFs have been evaluated in terms of their morphologies, thermal stability, crystallinity, and specific surface areas. Brunauer-Emmett-Teller (BET) surface areas of 1004 m2 g-1 to 1231 m2 g-1 were recorded across the synthesized MOFs. The MOFs were evaluated for their ability to adsorb commonly used harmful dyes, specifically cationic dye Methylene Blue and anionic dye Methyl Orange. The adsorption performances on MB and MO of as-synthesized MOFs were determined to be ranging from 190.1 to 262.5 mg g-1 and 244.5 to 296.7 mg g-1 respectively, demonstrating the potential of upcycling solar panels waste to valuable metal-organic framework for wastewater remediation. The findings pave the way for utilising solar panel electronic waste as a valuable resource for upcycled applications. National Environmental Agency (NEA) National Research Foundation (NRF) This research/project is supported by the National Research Foundation, Singapore, and National Environment Agency, Singapore under its Closing the Waste Loop Funding Initiative (Award No. USS-IF-2018-4).

Published
2022

38. Synthesis of n-dodecylamine borane C12H25NH2BH3, its stability against hydrolysis, and its characterization in THF

Author

Umit B. Demirci, Kevin Turani-I-Belloto, Eddy Petit, Antigoni Theodoratou, Sandrine Dourdain, Johan G. Alauzun, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut Européen des membranes (IEM), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), and ANR-18-CE05-0032,REVERSIBLE,BCN pour un stockage REVERSIBLE de H2(2018)

Subjects
chemistry.chemical_classification, 010405 organic chemistry, Hydrogen bond, Organic Chemistry, Boranes, Borane, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Analytical Chemistry, Inorganic Chemistry, Solvent, chemistry.chemical_compound, chemistry, Polymer chemistry, Anhydrous, Molecule, [CHIM]Chemical Sciences, Amine gas treating, Spectroscopy, Alkyl, ComputingMilieux_MISCELLANEOUS
Abstract

Dihydrogen Hδ+⋅⋅⋅Hδ− bonding that is accepted as an important unconventional hydrogen bonding could play a key role in molecular self-assembly of amine boranes. It is with this goal in mind that we have studied the behavior of n-dodecylamine borane nC12H25NH2BH3 (C12AB) dissolved in anhydrous THF. C12AB can be easily synthesized with a purity higher than 99% by Lewis acid-base reaction of a BH3 complex with n-dodecylamine nC12H25NH2. It is stable when dissolved in THF that is a good solvent of it. However, it is unstable in the presence of moisture, readily hydrolyzing and producing water-soluble borates. Molecular self-assembly of C12AB has thus to be studied in anhydrous conditions, which allows observing by DLS and SAXS-WAXS the formation of core-shell aggregates in anhydrous THF. The aggregates consist of about five self-assembling stretched C12AB molecules where the NH2BH3 groups are in the core of 3 A and the alkyl chains in an outer-shell.

Published
2022

39. Modélisation de la coalescence : connecter les échelles (de l'approche déterministe à l'approche stochastique)

Author

Hilaire, Lolita, STAR, ABES, Modélisation Mésoscopique et Chimie Théorique (LMCT), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Université de Montpellier, Jean-François Dufrêche, and Sophie Charton

Subjects
Chimie Séparative, Liquid-Liquid flow, Separation chemistry, Coalescence de gouttes, Droplet Coalescence, Physico-Chemistry of interfaces, Molecular dynamics, Modelling, Physico-Chimie des interfaces, Ecoulement liquide-Liquide, Modélisation, [CHIM.OTHE] Chemical Sciences/Other, Dynamique moléculaire, [CHIM.OTHE]Chemical Sciences/Other
Abstract

Coalescence plays a fundamental role in many industrial processes such as liquid-liquid extraction. It is a complex multi-scale phenomenon that relies on the interaction between deformable droplets that might be subjected to a flow. Understanding the phenomena involved in liquid-liquid extraction is necessary for the development and the optimization of treatment and recycling processes in the nuclear industry. However, the coalescence process remains poorly understood, especially at the nanoscale. In this thesis, coalescence is studied at the molecular scale by means of molecular dynamics simulations in order to connect the different scales. To that aim, several axes of work are developed.The first axis deals with the interaction between an AFM tip and a liquid film deposited on a substrate. This is a simple case compared to the liquid-liquid coalescence because one of the droplets (the AFM tip) is rigid, and the intermediate medium is gaseous. The results show that the surface fluctuations cause an instability of the interface deformation and are responsible of the jump-to-contact phenomenon in which the liquid enters in contact with the tip. Our results, on an experimentally observable system, have confirmed the validity and the limitations of continuous models. These models do not account for fluctuations, for the description of phenomena at the interfaces observed in AFM, but more generally for coalescence.The second axis concerns the study of the drainage of the interfacial film. An original approach is proposed, in which planar layers of water and heptane are constructed and stacked under periodic conditions. The two liquids are subjected to flows in opposite directions. The velocity profiles obtained in the molecular dynamics simulations are used to assess the effective viscosity of films confined between two liquid phases and to study the slip at the interfaces. Our results show that there is a significant slip at the liquid-liquid interface. The values of the slip lengths are related to the respective viscosities of the two liquids. This slip located at the liquid-liquid interfaces plays an important role during coalescence since it accelerates the film drainage.Finally, we study the stochastic effects controlling the formation of the liquid bridge through a series of simulations of coalescence of heptane drops in water. The simulation box is the same in each case, but a random perturbation is introduced by the Lyapunov instability, allowing the obtention of a set of closely related initial states having divergent trajectories. From this series of simulations we have established that the probability of coalescence as a function of time follows a Poisson distribution.In summary, we have proposed an original description of coalescence at the molecular scale using a probabilistic model describing the coalescence time and a hydrodynamic model describing the drainage at the molecular scale. Our study opens many perspectives for the simulation of coalescence in continuous approaches used in fluid mechanics and chemical engineering. It is also applicable to other physical problems whose kinetics are governed by the molecular scale., La coalescence joue un rôle fondamental dans de nombreux procédés industriels tels que l’extraction liquide-liquide. Il s’agit d’un phénomène multi-échelle complexe qui repose sur l'interaction entre des gouttes déformables, parfois soumises à un écoulement. Comprendre les phénomènes mis en jeu lors de l’extraction liquide-liquide est nécessaire au développement et à l’optimisation des procédés de traitement et de recyclage dans l’industrie nucléaire. Toutefois, le processus de coalescence reste à ce jour mal compris, en particulier à l’échelle nanométrique. Dans cette thèse, la coalescence est étudiée à l’échelle moléculaire par le biais de simulations de dynamique moléculaire, dans le but de faire le lien entre les différentes échelles. Pour répondre à cet objectif, plusieurs axes de travail sont développés.Le premier axe porte sur l'interaction entre une pointe AFM et un film liquide déposé sur un substrat. Il s'agit d'un cas simple en comparaison de la coalescence liquide-liquide, car une des gouttes (la pointe AFM) est rigide, et le milieu intermédiaire est gazeux. Les résultats montrent que les fluctuations de surface provoquent une instabilité de la déformation de l'interface et sont à l'origine du phénomène de saut (en anglais jump to contact) par lequel le liquide entre en contact avec la pointe. Nos résultats, sur un système observable expérimentalement, ont confirmé la validité et les limites des modèles continus, ne rendant pas compte des fluctuations, pour la description de phénomènes aux interfaces observés en AFM, et plus généralement pour la coalescence.Le second axe porte sur l’étude du drainage du film interfacial. Une approche originale est proposée, dans laquelle des couches planes d'eau et d'heptane sont construites et empilées en conditions périodiques. Les deux liquides sont soumis à des forces d'écoulement de sens opposés. Les profils de vitesse obtenus dans les simulations de dynamique moléculaire permettent de rendre compte de la viscosité effective des films confinés entre deux phases liquides et d'étudier le glissement aux interfaces. Nos résultats montrent qu'il y a un glissement important à l'interface liquide-liquide, que ce soit de l'eau sur l'heptane ou de l'heptane sur l'eau. Le rapport des longueurs de glissement est égal au rapport des viscosités des deux liquides. Ce glissement présent aux interfaces liquide-liquide joue un rôle important lors de la coalescence, puisqu'il accélère le drainage du film.Enfin, nous étudions les effets stochastiques contrôlant la formation du pont liquide à travers une série de simulations de coalescence de gouttes d'heptane dans l'eau. La boîte de simulation est la même dans chaque cas, mais une perturbation aléatoire est introduite par l'instabilité de Lyapunov, permettant d'imposer des états initiaux très proches mais des trajectoires divergentes. À partir de cette série de simulations nous avons établi que la probabilité de coalescence en fonction du temps suit une loi de Poisson.En résumé, nous avons proposé une description originale de la coalescence à l'échelle moléculaire à l'aide d'un modèle probabiliste décrivant le temps de coalescence et d'un modèle hydrodynamique décrivant le drainage à l'échelle moléculaire. Notre étude ouvre de nombreuses perspectives pour la simulation de la coalescence dans les approches continues utilisées en mécanique des fluides et en génie des procédés. Elle est également applicable à d'autres problèmes physiques dont la cinétique est gouvernée par l'échelle moléculaire.

Published
2022

40. Microemulsion as model to predict free energy of transfer of electrolyte in solvent extraction

Author

Jean-François Dufrêche, Thomas Zemb, Simon Gourdin-Bertin, Magali Duvail, Modélisation Mésoscopique et Chimie Théorique (LMCT), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), ANR-18-CE29-0010,MULTISEPAR,Modelisation multi-échelle des phases organiques pour l'extraction liquid-liquide(2018), European Project: 320915,EC:FP7:ERC,ERC-2012-ADG_20120216,REE-CYCLE(2013), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), and Université de Montpellier (UM)

Subjects
General Chemical Engineering, Thermodynamics, 02 engineering and technology, Electrolyte, 010402 general chemistry, 01 natural sciences, symbols.namesake, thermodynamics, Phase (matter), Microemulsion, Aqueous solution, Chemistry, Extraction (chemistry), Langmuir adsorption model, General Chemistry, 021001 nanoscience & nanotechnology, solvent extraction, 0104 chemical sciences, Solvent, Condensed Matter::Soft Condensed Matter, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Volume fraction, symbols, 0210 nano-technology, mesoscopic modelling
Abstract

Special Issue on Hierarchical Organization in Solvent Extraction; International audience; We consider here the extraction of metals in the form of salts transferred from an aqueous to a solvent phase. Extraction is triggered by complexation and quenched by the associated necessary reorganization of the structured solvent phase. The extraction of ions changes the relative fraction of extractant molecules that is not part of the highly curved surfactant monolayer and is dispersed molecularly in the oil, and also the polar volume fraction including co-extracted water. The free energy and corresponding microstructures of the water-poor microemulsions are modelled in the frame of the Gaussian random fields (GRF) model. The curvature frustration energy significantly contributes to the free energy of extraction. A typical example of predicted isotherm using the GRF model is compared to the classically considered supramolecular complex formation, together with a minimal Langmuir model and an explicit monomer-to-film equilibrium of amphiphilic extractant. The corresponding small-angle scattering spectra and morphology changes are shown. One implication is that selectivity between a hydrated and a non-hydrated species is concentration dependent and cannot be considered as a constant as a function of the extractant concentration.

Published
2022

41. In Vivo Biotransformations of Indium Phosphide Quantum Dots Revealed by X-Ray Microspectroscopy

Author

Wai Li Ling, Peter Reiss, Giulia Veronesi, Lucia Mattera, Giada Onorato, Karl David Wegner, Claudia Tortiglione, Hiram Castillo-Michel, María Moros, Groupe modélisation et chimie théorique (MCT), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), European Synchrotron Radiation Facility (ESRF), Istituto di Scienze Applicate e Sistemi Intelligenti ' E. Caianiello', Consiglio Nazionale delle Ricerche, Aragon Materials Science Institute and Ciber-BBN, Laboratoire d'Electronique Moléculaire Organique et Hybride (LEMOH), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS), Structures et propriétés d'architectures moléculaire (SPRAM - UMR 5819), Institut Nanosciences et Cryogénie (INAC), Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de biologie structurale (IBS - UMR 5075 ), Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Synthèse, Structure et Propriétés de Matériaux Fonctionnels (STEP), Département Interfaces pour l'énergie, la Santé et l'Environnement (DIESE), Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Agence Nationale de la Recherche (France), European Commission, Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (Brasil), Veronesi, Giulia, Reiss, Peter, Wegner, Karl David, Li Ling, Wai, Tortiglione, Claudia, Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), ANR-16-CE09-0015,NEUTRINOS,Suivi des interactions biologiques par détection optique ultrasensible à base de nanoparticules(2016), Veronesi, Giulia [0000-0001-9228-6082], Reiss, Peter [0000-0002-9563-238X], Wegner, Karl David [0000-0003-0517-1880], Li Ling, Wai [0000-0002-4264-5750], and Tortiglione, Claudia [0000-0003-1447-7611]

Subjects
0106 biological sciences, 0301 basic medicine, Biodistribution, Fluorescence-lifetime imaging microscopy, [SDV.BIO]Life Sciences [q-bio]/Biotechnology, Materials science, X-Ray Fluorescence imaging, Biocompatibility, Hydra, Phosphines, [SDV.IB.IMA]Life Sciences [q-bio]/Bioengineering/Imaging, chemistry.chemical_element, quantum dots, Indium phosphide, Indium, 010603 evolutionary biology, 01 natural sciences, 03 medical and health sciences, chemistry.chemical_compound, In vivo, in vivo, Animals, General Materials Science, Hydra vulgaris, biology, Quantum dots, X-ray absorption spectroscopy, Spectrometry, X-Ray Emission, indium phosphide, [CHIM.MATE]Chemical Sciences/Material chemistry, biology.organism_classification, 3. Good health, X-ray Absorption Spectroscopy, 030104 developmental biology, chemistry, Quantum dot, Biophysics
Abstract

Many attempts have been made to synthesize cadmium-free quantum dots (QDs), using nontoxic materials, while preserving their unique optical properties. Despite impressive advances, gaps in knowledge of their intracellular fate, persistence, and excretion from the targeted cell or organism still exist, precluding clinical applications. In this study, we used a simple model organism (Hydra vulgaris) presenting a tissue grade of organization to determine the biodistribution of indium phosphide (InP)-based QDs by X-ray fluorescence imaging. By complementing elemental imaging with In L-edge X-ray absorption near edge structure, unique information on in situ chemical speciation was obtained. Unexpectedly, spectral profiles indicated the appearance of In-O species within the first hour post-treatment, suggesting a fast degradation of the InP QD core in vivo, induced mainly by carboxylate groups. Moreover, no significant difference in the behavior of bare core QDs and QDs capped with an inorganic Zn(Se,S) gradient shell was observed. The results paralleled those achieved by treating animals with an equivalent dose of indium salts, confirming the preferred bonding type of In3+ ions in Hydra tissues. In conclusion, by focusing on the chemical identity of indium along a 48 h long journey of QDs in Hydra, we describe a fast degradation process, in the absence of evident toxicity. These data pave the way to new paradigms to be considered in the biocompatibility assessment of QD-based biomedical applications, with greater emphasis on the dynamics of in vivo biotransformations, and suggest strategies to drive the design of future applied materials for nanotechnology-based diagnosis and therapeutics., K.D.W. and L.M. thank the Labex SERENADE (grant Saquado) and the French National Research Agency ANR (grant no. ANR-12-NANO-0007-03 NanoFRET) for funding. P.R. acknowledges financial support from Labex ARCANE (grant QDPhotocat), from CAPES/COFECUB (grant 858/15), and from ANR (grant number ANR-16-CE09-0015-03 Neutrinos). M.M. acknowledges financial support from the European Union’s Horizon 2020 research and innovation programme (Marie Skłodowska-Curie grant agreement no. 660228) and Spanish Juan de la Cierva subprogram.

Published
2019

42. Effect of alkyl chains configurations of tertiary amines on uranium extraction and phase stability – part II: Curvature free energy controlling the ion transfer

Author

Zijun Lu, Sandrine Dourdain, Jean-François Dufrêche, Bruno Demé, Thomas Zemb, Stéphane Pellet-Rostaing, Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Modélisation Mésoscopique et Chimie Théorique (LMCT), and Institut Laue-Langevin (ILL)

Subjects
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Materials Chemistry, Physical and Theoretical Chemistry, Condensed Matter Physics, Spectroscopy, Atomic and Molecular Physics, and Optics, Electronic, Optical and Magnetic Materials
Abstract

International audience; We consider a structural and thermodynamic analysis of uranium solvent extraction by tertiary amines for which the alkyl chain configuration has been modified. The first part of this work revealed that tertiary amines with longer or branched alkyl chains allow tuning the phase stability and uranium extraction by modifying the volume of the polar species extracted in the organic phase. A complete fit of SANS data confirms in this second part that this phenomenon is related to the supramolecular self-assembly of the tertiary amines into smaller reverse micelle like aggregates for longer or branched alkyl chains. It moreover shows that these smaller aggregates quench third phase formation thanks to reduced attractive interactions between them. A thermodynamic analysis based on the “ienaic” approach further rationalizes this effect by showing that alkyl chains have a significant effect on the aggregate’s curvature free energy. The latter becomes a predominant inhibitor of uranium free energy of transfer due to the high entropic contribution originated by the extractants branching and packing.

Published
2022

43. Impact of impurities on the fabrication and performances of yttrium-doped thoria electrolyte ceramics

Author

CLAVIER, Nicolas, Cherkaski, Yanis, BRISSONNEAU, Laurent, Dacheux, Nicolas, Interfaces de Matériaux en Evolution (LIME), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Laboratoire de Maitrise de la contamination et de la Chimie des Caloporteurs et du Tritium (LMCT), Service Mesures et modélisation des Transferts et des Accidents graves (SMTA), Département Technologie Nucléaire (DTN), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Département Technologie Nucléaire (DTN), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)

Subjects
Nuclear and High Energy Physics, technology, industry, and agriculture, Sodium corrosion, Yttrium-doped thoria, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Nuclear Energy and Engineering, Electrical properties, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], General Materials Science, Oxygen monitoring sensors, 0210 nano-technology, Impurities
Abstract

International audience; The effect of several impuritites on the life-cycle of yttria-doped thoria electrolyte was evaluated in this study. All the oxide exhibited the single-phase fluorite-type structure expected for such materials, while the variation of the unit cell parameter attested for the incorporation of the impurities in the lattice. Doping with 0.2, 0.5 or 1 wt.% of Al, Si or Zr only slightly affected the morphology of the powders, as well as the microstructure of the pellets obtained after sintering, even if a deleterious effect, leading to the embrittlement of the samples, was observed for high silicon contents. The presence of silicon and zirconium in the ceramic further modified its electrical properties. The grain conductivity was always found to decrease. Impedance spectroscopy also revealed a strong modification of the signal assigned to grain boundaries, which evidenced that impurities partially migrated during the sintering step. Finally, corrosion tests undertaken in liquid sodium at 500°C showed that the pellets were fragilized by the presence of silicon or high zirconium contents, possibly through the formation of Na2MO3 ternary oxides at the grain boundaries. From a general point of view, silicon seems to be the most harmful impurity that should be especially checked during the fabrication processes.

Published
2022

44. Molecular dynamics simulations of Eu(NO3)3 salt with DMDOHEMA in n-alkanes: Unravelling curvature properties in liquid-liquid extraction

Author

Simon Stemplinger, Magali Duvail, Jean-François Dufrêche, Modélisation Mésoscopique et Chimie Théorique (LMCT), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), ANR-18-CE29-0010,MULTISEPAR,Modelisation multi-échelle des phases organiques pour l'extraction liquid-liquide(2018), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), and Université de Montpellier (UM)

Subjects
Lanthanide, Materials science, Thermodynamics, Flexural rigidity, Rigidity (psychology), 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, Diluent, Micelle, Atomic and Molecular Physics, and Optics, 0104 chemical sciences, Electronic, Optical and Magnetic Materials, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Molecular dynamics, Yield (chemistry), Materials Chemistry, Physical and Theoretical Chemistry, Umbrella sampling, 0210 nano-technology, Spectroscopy
Abstract

The spontaneous packing parameter and the bending rigidity of small reverse aggregates similar to reverse micelles in different diluents have been investigated. The considered system consisting of a common extractant (DMDOHEMA), a lanthanide salt (Eu(NO3)3) and water in various n-alkanes (n-heptane, n-nonane and n-dodecane) has been studied using molecular dynamics simulations to the obtain penetration behavior of different diluents. Umbrella sampling and fluctuation theory have been used to yield the bending rigidity. Different approaches for the determination of the packing parameter have been applied. For the most reproducible methodology a spontaneous packing parameter of 4.6 and an effective rigidity constant of 50 k B T per extractant molecule has been found.

Published
2022

45. Effect of Al3+ and Mg2+ on the flotation of fluorapatite using fatty- and hydroxamic-acid collectors – A multiscale investigation

Author

Amir Eskanlou, Michael Badawi, Alessandra Romero, Qingqing Huang, Yann Foucaud, West Virginia University [Morgantown], Modélisation Mésoscopique et Chimie Théorique (LMCT), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Laboratoire de Physique et Chimie Théoriques (LPCT), and Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[PHYS]Physics [physics], chemistry.chemical_classification, integumentary system, Metal ions in aqueous solution, Fluorapatite, Inorganic chemistry, General Physics and Astronomy, Fatty acid, Context (language use), Surfaces and Interfaces, General Chemistry, Condensed Matter Physics, Apatite, Surfaces, Coatings and Films, Adsorption, chemistry, visual_art, visual_art.visual_art_medium, [CHIM]Chemical Sciences, Froth flotation, Selectivity, ComputingMilieux_MISCELLANEOUS
Abstract

Fluorapatite flotation is influenced by the dissolved lattice metal ions. Al3+ and Mg2+ from the associating gangue minerals influence the adsorption of collector molecules onto the fluorapatite surface during flotation. Hence, unveiling new insights on such interactions in the context of froth flotation at an atomic level paves the way for improving flotation selectivity. An original multiscale approach has been developed involving flotation experiments, electro-kinetic and adsorption density measurements, X-ray photoelectron spectroscopy studies, and density functional theory simulations. Fatty acid establishes an enhanced interaction with the bare apatite surface compared to the hydroxamates. Na+ counter-ion contributes to the adsorption of fatty acid on bare apatite. Both Al3+ and Mg2+ ions are beneficial for the adsorption of fatty acid, thereby the fluorapatite flotation. For octanohydroxamic acid, the presence of Al3+ results in a stronger collector-apatite interaction, and therefore an enhanced flotation. For fatty acid and hydroxamates, adsorption of Mg2+ leads to an improved collector-apatite interaction. Benzohydroxamic acid is more vigorously adsorbed than octanohydroxamic acid in the presence of Mg2+. Fatty acid establishes a stronger interaction with bare and Al3+/Mg2+-treated fluorapatite, as opposed to hydroxamates. Mg2+ is more favorable than Al3+ in fluorapatite flotation using both fatty acid and hydroxamates.

Published
2022

46. Diluent effects on the stability range of w/o micellar systems and microemulsions made with anionic extractants

Author

El Maangar, Asmae, Lopian, Tobias, Dourdain, Sandrine, Kunz, Werner, Zemb, Thomas, Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), University of Regensburg, Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), This work has been made due thanks a special funding 'these phare amont-aval' attributed by Yves Brechet, High commissar of CEA., and The SANS was performed via the fast test access at ILL D11 ILL AGA EASY-887

Subjects
[PHYS]Physics [physics]
Abstract

International audience; Here we present a series of complete phase prisms for water, an organic diluent and di-(2-ethylhexyl) phosphoric acid (HDEHP), one of the most widely used double-branched lipophilic surfactants in hydrometallurgy. Partial or total titration with sodium hydroxide evidence that the mole fraction of the counter-cation “Z” is the variable that controls the packing and spontaneous curvature of the curved film formed by this extractant. Penetrating solvents such as toluene and iso-octane and the non-penetrating solvent dodecane as well as common hydrotropes acting as co-solvents, are considered. The three classical cuts of the phase prism are shown. The regions for which liquid–liquid extraction is possible are determined, as well as the location of the liquid crystals at the origin of the often observed third-phase formation. It is shown that profoundly different trends are obtained when replacing the common solvents currently used in hydrometallurgical processes with hydrotropes.

Published
2022

47. Highly-Selective Optoelectronic Nose Based on Surface Plasmon Resonance Imaging for Sensing Volatile Organic Compounds

Author

Sophie Brenet, Benjamin Musnier, Cyril Herrier, Aurelian John-Herpin, Tristan Rousselle, François-Xavier Gallat, Arnaud Buhot, Yanxia Hou, Thierry Livache, Chimie pour la Reconnaissance et l’Etude d’Assemblages Biologiques (CREAB), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS), Structures et propriétés d'architectures moléculaire (SPRAM - UMR 5819), Institut Nanosciences et Cryogénie (INAC), Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Aryballe Technologies, Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Carbon atom, Chemistry, business.industry, Kinetic information, 010401 analytical chemistry, High selectivity, 02 engineering and technology, Performance gap, 021001 nanoscience & nanotechnology, Highly selective, 01 natural sciences, 0104 chemical sciences, Analytical Chemistry, Gas phase, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Surface plasmon resonance imaging, Optoelectronics, 0210 nano-technology, Ternary operation, business
Abstract

International audience; Monitoring volatile organic compounds (VOCs) is an important issue, but difficult to achieve on a large scale and on the field using conventional analytical methods. Electronic noses (eNs), as promising alternatives, are still compromised by their performances due to the fact that most of them rely on a very limited number of sensors and use databases devoid of kinetic information. To narrow the performance gap between human and electronic noses, we developed a novel optoelectronic nose, which features a large sensor microarray that enables multiplexed monitoring of binding events in real-time with a temporal response. For the first time, surface plasmon resonance imaging is demonstrated as a promising novel analytical tool for VOC detection in the gas phase. By combining it with cross-reactive sensor microarrays, the obtained optoelectronic nose shows a remarkably high selectivity, capable of discriminating between homologous VOCs differing by only a single carbon atom. In addition, the optoelectronic nose has good repeatability and stability. Finally, the preliminary assays using VOC binary and ternary mixtures show that it is also very efficient for the analysis of more complex samples, opening up the exciting perspective of applying it to “real-world” samples in diverse domains.

Published
2018

48. Preferential Adsorption in Mixed Electrolytes Confined by Charged Amorphous Silica

Author

Jean-François Dufrêche, Bertrand Siboulet, Remco Hartkamp, Johannes Lützenkirchen, JT Johan Padding, Max F. Döpke, Othonas A. Moultos, Delft University of Technology (TU Delft), Karlsruher Institut für Technologie (KIT), Modélisation Mésoscopique et Chimie Théorique (LMCT), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Aqueous solution, 02 engineering and technology, Electrolyte, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Ion, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Colloid, General Energy, Solvation shell, Adsorption, Chemical physics, Surface roughness, Physical and Theoretical Chemistry, 0210 nano-technology, Vicinal
Abstract

Preferential ion adsorption in mixed electrolytes plays a crucial role in many practical applications, such as ion sensing and separation and in colloid science. Using all-atom molecular dynamics simulations of aqueous NaCl, CaCl2, and NaCl-CaCl2 solutions confined by charged amorphous silica, we show that Na+ ions can adsorb preferentially over Ca2+ ions, depending on the surface structure. We propose that this occurs when the local surface structure sterically hinders the first hydration shell of the Ca2+ ion. Introducing a protrusion metric as a function of protrusion of deprotonated silanols, ion-specificity is successfully predicted on isolated, vicinal, and geminal silanols alike, provided that no other deprotonated silanols are found nearby. Furthermore, we introduce a new strategy to analyze the results as a function of distance from the surface. This approach effectively removes surface roughness effects allowing for direct comparison with classical electric double layer theory and distinction of specifically adsorbed ions and electrostatically adsorbed ions.

Published
2019

49. Molecular Dynamics Simulation of Mesoporous Silica under Ionic Ballistic Irradiations

Author

Lou, Yu, Siboulet, Bertrand, Dourdain, Sandrine, Deschanels, Xavier, Delaye, Jean-Marc, Modélisation Mésoscopique et Chimie Théorique (LMCT), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Tri ionique par les Systèmes Moléculaires auto-assemblés (LTSM), Nanomatériaux pour l'Energie et le Recyclage (LNER), Département de recherche sur les Procédés et Matériaux pour les Environnements complexes (DPME), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)

Subjects
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry
Abstract

International audience; We performed simlulations of irradiation of silica mesoporous samples. We use DL_POLY 3 along with ZBL potentials. Irradiation results in a density modification which which trace versus the deposited energy. We alternate displacements cacsade with relaxation periods. We plot pressure variation and analyse the coordination.

Published
2019

50. Vibrating Magnetic Particles for Cancer Cells Destruction

Author

Morel, R., Caroline Thébault, Cécile Naud, Hélène Joisten, Selma Leulmi, Cécile Iss, Mélissa Morcrette, Guillaume Ortiz, Yanxia Hou, Thierry Livache, Roberto Calemczuk, Marie Carrière, Philippe Sabon, Isabelle JOUMARD, Stéphane Auffret, Bernard Dieny, SPINtronique et TEchnologie des Composants (SPINTEC), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Groupement de recherches de Lacq (GRL), Arkema (Arkema), Chimie pour la Reconnaissance et l’Etude d’Assemblages Biologiques (CREAB), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS), Structures et propriétés d'architectures moléculaire (SPRAM - UMR 5819), Institut Nanosciences et Cryogénie (INAC), Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie Interface Biologie pour l’Environnement, la Santé et la Toxicologie (CIBEST ), HOU-BROUTIN, Yanxia, Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[PHYS]Physics [physics], ComputingMilieux_MISCELLANEOUS, [PHYS] Physics [physics]
Abstract

International audience

Published
2018

Catalog

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